Mineral oil composition



Patented Apr. 1940 PATENT OFFICE MINERAL OIL COMPOSITION tion of NewYork No Drawing. Application May 26, 1938, Serial No. 210,160

28 Claims.

This invention has to do ina general way with mineral oil compositionsand is more particularly related to compositions comprised of mineraloil and a minor proportion of an added ingredient which will improve theoil in one or more important respects.

It is well known to those familiar with the art that mineral oilfractions refined for their various uses are in and of themselvesusually deficient in one or more respects, so that their practicalutility is limited even in the particular field for which they have beenrefined. For example, mineral oil fractions refined for use aslubricants have a tendency to oxidize under conditions of use with theformation of sludge or acidic oxidation products; also the lighterfractions such as gasoline and kerosene tend to oxidize with theformation of color bodies, gum, etc. In order to prevent the formationof these products and thereby extend the useful life of the oilfraction, it is common practice to blend with such oil fractions anadditive ingredient which will have the effect of inhibiting oxidation,such ingredients being generally known to the trade as oxidationinhibitors or sludge inhibitors, gum inhibitors, etc.

It is also the practice to add other ingredients to mineral oilfractions for the purpose of improving oiliness characteristics and thewear-reducing action of such mineral oils when they are used aslubricants, particularly when the oils are used for the purpose oflubricating metal surfaces which are engaged under extremely highpressures and at high rubbing speeds.

Other ingredients have been developed for the purpose of depressing thepour/point of mineral oil fractions which have been refined for use aslubricants, such refinement leaving a certain amount of wax in the oil,which, without the added ingredient, would tend to crystallize attemperatures which render theoil impracticable for use'under lowtemperature conditions. Additivejagents have also been developed forimproving'jfthe'viscosity index of lubricating oil fractions.

intliegcase of internal combustion engines, par- '45 ticuI rly'thoseoperating with .high cylinder pressures,'there is a decided tendency forthe ordinary lubricating oil fractions to form, under such conditions ofuse, carbonaceous deposits which cause the piston rings to becomestuckin their slots and which fill the slots in the oil ring or rings,

thus materially reducing the efficiency of the engine. Ingredients havetherefore been developed which, when added to the oil, will reduce thenatural tendency of the oil to form deposits which interfere with thefunction of the piston rings.

Aside from the corrosive action which attends the formation of acidicproducts of oxidation in mineral oil fractions of the lubricant range,it has been discovered that certain types of recently developed hardmetal alloy bearing metals, such 10 as cadmium-silver alloy bearings,are attacked by ingredients in certain types of oils, particularly oilsof high viscosity index obtained by various methods of solvent refining.This corrosive action on alloys of the above type has led to thedevelopment of corrosion inhibitors which may be used in solvent-refinedoils to protect such bearing metals against this corrosive action.

In the lighter mineral oil fractions, such as those used for fuelpurposes, particularly in internal combustion engines, it has been foundthat 20 the combustion characteristics of the fuel may be controlled andimproved by adding minor proportions of various improving agentsthereto.

The various ingredients which have been de-' veloped for use in mineraloil fractions to im- 5 prove such fractions in the various respectsenumerated above are largely specific to their particular applications,and it has therefore been the practice to add a separate ingredient foreach 30 of the improvements which is to be effected.

It is a primary object of the present invention to provide a mineral oilcomposition which has been improved in one or more of the variousproperties enumerated above by the incorporation therein of a smallquantity of a multifunctional compound selected from that group or classof metal-organic compounds which may be designatedas the oil-soluble oroil-miscible metal salts of alkyl-substituted hydroxyaromatic carboxylicacids in which both the hydroxyl and the carboxyl hydrogens aresubstituted with metal, We have discovered that metal oxyaromatic-.-metal carboxylate' salts of the general class above referred to may beadded in small quantities to mineral oil fractions to form mineral oilcompositions or blends superior to the unblended fractions in one ormore important respects, and the present invention, therefore, isbroadly directed to clear hydrogen has been substituted with a metaloxygroup and another nuclear hydrogen is substituted with a carboxyl groupin which the carboxyl hydrogen has been replaced with its equivalentweight of metal. This characterizing group may be represented by theformula:

T (OM) (COOM') in which T represents an aromatic nucleus; (OM)represents at least one hydroxyl group the hydrogen of which is replacedby its equivalent weight of metal M; and COOM' represents at least onecarboxyl group in which the hydrogen is replaced with its equivalentweight of a metal,

7 M, which may be the same as, or different from,

the metal M. Both the (OM) group and the (COOM') group are attached tothe nucleus T.

The metal salts of hydroxyaromatic carboxylic acids of thetype'corresponding to thegroup-represented by the above formula whichare otherwise unsubstituted are not miscible with mineral oil, and it istherefore important'that the improving agents containing the abovecharacterizing group have additional nuclear hydrogen replaced withsubstituents of a solubilizing nature. In other words, it is importantthat the aryl nucleus carry asubstituent or substituents which willrender the composition as a whole miscible with mineral oil fractions.By the terms "oilmiscible or oil-soluble as they are used herein we havereference to that property of remaining uniformly dispersed in themineral, oil fraction either as a true solution or as a colloidalsuspension during normal conditions of handling and use.

The improving agents contemplated by this invention are characterized bythe presence of alkyl substituents in the aryl nucleus, and theimproving agents preferred for use in viscous mineral oils are furthercharacterized by the presence of alkyl or aliphatic substituents in thearyl nucleus which will give other properties to the com-' positionasa-whole in addition to oil-miscibility. We have found, for example,that where the aryl nucleus is substituted with one or more aliphaticgroups corresponding to certain aliphatic hydrocarbon compounds ofrelatively high molecular weight (herein referred to as' heavy alkylgroups), a compound or composition can be obtained which will efi'ectmarked improvement in the viscosity index and the pour point as well asother important properties of viscous mineral oils. I

As a general proposition, therefore, it may be said that the improvingagents contemplated by this invention are metal salts of hydroxyaromaticcarboxylic acid having the characterizing group T(OM) (COOM') describedabove, in which additional nuclear hydrogen is replaced with anoilsolubilizing substituent such as a predominantly aliphatic material,such substituent comprising a sufficient proportion of the compositionas a whole to render the same miscible with mineral oil fractions undernormal conditions of handling and use. As a further generalization itmay be said that at least one point on the aromatic nucleus T, andpreferably two or more points on such nucleus, are substituted withaliphatic hydrocarbon radicals 'or groups, such aliphatic rad- III.

icals or groups preferably being'high molecular weight-derivatives orheavy alkyl groups.

The simplest type of compound satisfying the above requisites may berepresented by the formula:

I. R(T(OM) (COOM')) in which R represents at least one aliphatichydrocarbon radical or group, such group or groups preferablycorresponding to relatively high molecular weight aliphatic hydrocarbonsand being attached to a mono or poly cyclic aromatic nucleus T andin,which (OM) and (COOM') are as indicated above.

In addition to the aliphatic or alkyl substituent R, the compounds orcompositions contemplated herein as'mineral oil improving agents mayhave additional nuclear hydrogen replaced with other substituents whichmay or may not have a solubilizing effect upon the composition as awhole. Such a compound in its simplest form may be represented by theformula:

II. R(T(OM) (COOM') Y) in which R, T, (OM) and (COOM') have the samesignificance indicated above and in which Y represents residual hydrogenwhich may be replaced by a radical from the group consisting of:chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro, and aminoradicals or groups. Compounds of the above general formula-type havingmono, di, and tri cyclic nuclei are illustrated by the followingspecific formulae:

R OM

in which'at least one R represents an aliphatic radical or group,preferably a heavy alkyl, group, and in which the remaining R'srepresent residual hydrogen which may be replaced with hydroxy,chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl, nitro and aminoradicals or groups.

In the foregoing examples it will be observed that the aliphatic orallgvl substituent is a monovalent aliphatic hydrocarbon group, but, aswill appear from the hereinafter described synthesis of ouroil-improving agent, part or all of the aliphatic hydrocarbon materialmay be comprised of polyvalent aliphatic hydrocarbon radicals or groupsin which the several valences are attached to separate aromatic nucleargroups. Compounds of this type are included under the following generalformula representation:

in which T, (OM), and (COOM') have the same significance indicatedabove; R. represents at least one aliphatic or alkyl radical or group,such alkyl group or groups being attached by one valence only to atleast one aromatic nucleus T, v

1 representing the valence of the aliphatic 'radi-.

the molecule represented by the formula whicharoma;

are attached to the aliphatic group or groups represented by R throughthe valences o.

In the foregoing general formula representation III it will be seen thatthe compounds represented thereby include those. materials in which allof the aliphatic substituent is monovalent (12:1 and n=1) or in whichall of the aliphatic 3 substituent is polyvalent (v-and n being equal totwo, three, or four); or since R is defined as being at least onealiphatic radical or group and may, therefore include several suchgroups, it will be seen that this general Formula 111 is inclusive ofcompounds having aliphatic groups or radicals of different valences(from one to four) in the same molecule. Also it will be observed thatsince n may be any whole number from one to four, the number of aromaticnuclei T in the molecule may likewisevary from one to four. It will beseen, therefore, that the relationship between n and v in Formula III,in itS 'b1O2-d6$t aspect, is such that when n is equal to one, u isequal to one; and when n is greater than one, the valence v of at leastone of the R's is equal to n (in order to tie the several nuclei or T'stogether), the valence of any remaining R's beingany whole number equalto or less than 11.

As stated above and as will appear more fully later from the descriptionof their synthesis, these materials represented'by general Formula IIImay contain both monovalent and polyvalent aliphatic substituents. Boththe polyvalent aliphatic substituent and the monovalent substituent, ifboth are present, may be introduced in the nucleus as part ofanalkylation reaction, or all or part of the monovalent aliphaticsubstituent may be present in the nucleus of a hydroxy-aromatic startingmaterial as low molecular weight aliphatic groups, such as methyl,ethyl, propyl groups, etc. 7

Compounds of the general type last described above, which includepolyvalent substituted aliphatic substituents and may also include boththe monovalent and the polyvalent substituents, are included under thesubgeneric formula representation:

in which T, (OM), and (COOM) have the samesignificance as indicatedabove; R represents at least one polyvalent aliphatic radical orgrouphaving a valence v of two, three, or four; Yb indicates the same groupof substituents as described above for Y; Rc represents monovalentaliphatic radicals or groups; b' represents the number 'of Ygys and isequal to zero or a whole number corresponding to the valences on thenucleus T not satisfied with R (OM), (COOM'), and Re; 0 indicates thenumber of RcS and is equal to zero or a whole number corresponding tothe valences on the nucleus T not satisfied with R (OM), (COOM'), andYe; and n represents a whole number from two to four and indicates thetotal number of the groups ('I(OM) (CO0M')Yb'Rc-) present in themolecule represented by theformula'which are attached to the aliphaticgroup or groups represented by R through the valencesv'.

In the abovgeneral-Formulae III and IV it will be understoo'ri'thatsince R and 13. are ali phatic hydrocarbon i radicals of the chain-type and are each 'attacl'iefl'by one valence onlyto each correspondingaromatic nucleus, the valence'v or v' of such'ra'dnumberofaromatkrnuclei inf- 5 uleanddn all or radicals is pf necessity.never. thef number 11, which indicates the Formula III is always equalto one when n equals one. Otherwise an R or an R having a valencegreater than the number (n or n) of aromatic nuclei would either havesome of its valences unsatisfied or else would form a condensed ring orrings byattachment at two or,m ore points to one and the same aromaticnucleus. Such latter compounds, as already indicated from the definitionof R or R are not considered as characterizing the product of thepresent invention although probably formed in some instances in minoramounts as unobjectionable by-products by I certain of the methods ofpreparation herein disclosed.

A simple type of COIIIDOUIld coming under general Formula III in which22 and n-is each equal to one and in which there is only oneoil-solubilizing aliphatic group R may be illustrated by the followingformula showing T for purposes of illustration as a monocyclic nucleus:

on COOM' 'one, it will be apparent that there may be more than one heavyalkyl substituent attached to the nucleus T. Such a compound, where vand n are each one and in which there are two such monolowing formula:

in which the chains and the substituent characters have the samesignificance defined above.

Compounds of the type satisfying the general Formula III and thesubgeneric Formula IV in which R (or R is polyvalent and v (or v) I andn- (or n) are more than one and in which there is only one suchpolyvalent R group may be illustrated by the following formula, in whichthe aryl nucleus T is again indicated for illustration as beingmonocyclic:

In the above formula 0, Re is a monovalent andj'sithe same asmonova'lent R in Formula III. Under this same type of compound indicatedV valent R groups, may be represented by the folalkyl'group as definedabove under Formula IV characterizing groups have the same significancedescribed above under Formula C.

H H H H H a no c c c on n I a M 000M 0 000M OM 000M A XX Y. -R. Yt"-- R.Irv-R. H 11 no 0 c on H H H H H The possible molecular structure ofcompounds in which the aryl nucleus T is polycyclic will be As to thepossible number of R (and Rc groups going to make up a single molecule,this will vary with the extent to which it is desired toeffectsubstitution of the nucleus with Oil-solubilizing aliphatic groups forobtaining the desired properties in the product and is, of course,limited by the number of valences on the aromatic nucleus which areavailable for substitution. -As

1 will be apparent to those skilled in the art, the

maximum possible number of R" (and RC) groups which can be attached to asingle aromatic nucleus will vary as the nucleus is mono or poly cyclicand also as the nucleus isotherwise substituted. It will also beapparent that available valences on the nuclei may all be attached topolyvalent aliphatic substituents.

It will be understood that the oil-improving agents contemplated by thisinvention may be pure compounds satisfying the general Formula IIIdescribed above with any one of the various mono and poly cyclicaromatic nuclei as T and the various. substituents R (or R and Y)described, the only requisites being that at least one nuclear hydrogenbe substituted with a metal-oxy (OM) group, at least one nuclearhydrogen be substituted with a (COOM') group, and at least one nuclearhydrogen be substituted with an oil-solubilizing aliphatic radical orgroup. However, in manufacturing the preferred oilimproving product ofthe present invention by the preferred methodv of procedure, as willappear more fully later on, the final oil-improving product obtained isnormally or usually a mixture of different compounds corresponding todifferent values of n and o and to different num-- bers of aliphaticgroups R As has been emphasized hereinabove, it is im-,

portant that the oil-improving agents as represented by general FormulaeIII and IV have nuclear hydrogen in the aromatic nucleus T substitutedwith predominantly aliphatic material which comprises a sufficientproportion of the composition as a whole to render the same misciblewith the mineral oil fraction in which the improving agent is used undernormal conditions of handling and use. It appears from the results ofour research that there is a critical range in the degree of alkylationof these improving agents below which the product or agent will notsatisfy the requirements for oil-miscibility. Expressing this in anotherway, it appears that the hydroxyaromatic constituent of the alkylatedhydroxyaromatic compound from which the alkylated metaloxyaromatic-metalcarboxylate salt is derived should not exceed a certain percentage ofsuch alkylated hydroxyaromatic composition as a whole. This criticalrange of alkylation may be roughly expressed as the ratio by weight of(T(OH))n to R (T(OH))n.

The degree of alkylation and the critical ranges within which operativeand preferred compounds can be obtained may also be expressed as thenumber of carbon atoms contained in the aliphatic substituents for eacharyl nucleus in a given molecule or molecular structure.

The criticalrange in the degree of alkylation of the aryl nucleus in theimproving agents contemplated herein may vary with: (a) the mineral oilfraction in which the improving agent is to be used; (12) the arylnucleus T (mono or poly cyclic); (c) the hydroxyl content of the arylnucleus from which the final product is obtained (mono or polyhydric);(d) the character of aliphatic material comprising the substituent(straight or branched chain); (c) mono or poly substitution of the arylnucleus; and (f) other substituents on the nucleus T, which may be ofpositive or negative or of neutral solubilizing activity.

In general it may be said that a, polycyclic nucleus appears to requirea higher degree of alkylation than a monocyclic nucleus; that apolyhydric nucleus requires a higher degree of alkylation than amonohydric nucleus; and that branched chain aliphatic substituents havea somewhat greater solubilizing action than straight chain solubilizingsubstituents.

In view of the foregoing variables it would be impracticable andprobably misleading to attempt to give an expression and figure whichwould indicate accurately the proper ratio of hydroxyaromaticconstituent to the alkylated hydroxyaromatic constituent which wouldexpress a degree of aliphatic substitution satisfying all cases takingthese variables into account. As a guide for preparing these improvingagents, however, our research indicates that for a product having pourdepressing and V. I. improving properties in addition to other valuableproperties the ratio, expressed as:

'r on VII. aw

should not be greater than .17 when the weight .of the hydroxyaromaticnucleus or component net to the corresponding alkylated hydroxyaromaticnucleus or component therein should not be greater than about seventeenparts by weight of the former to about 100 parts by weight of thelatter, or about seventeen per cent, when the weight of thehydroxyaromatic nucleus or component is expressed in terms of itschemically equivalent weight of phenol. It will be observed that theratio as represented by the Formula VII does not take into account anyother substituent in the nucleus than the allphatic substituents and thehydroxyl group; but since the aliphatic substituent is primarily reliedupon in the agents contemplated herein as the solubilizing substituent,it is believed that the foregoing expression and limits will serve as aworking guide for the preparation of oil-soluble materials and thepreferred multifunctional materials.

As stated above, the degree of alkylation may also be expressed by thenumber of carbon atoms contained in the aliphatic substituent for agiven hydroxyaromatic nucleus T. As a general guide here it may be saidthat the aliphatic substituents represented by R" in the above generalFormula III should, for the preferred multifuctional materialscontemplated herein, contain at least thirty carbon atoms for eacharomatic nucleus T.

The ratio of seventeen per cent, which we may term the phenolic ratio,represents what we consider a maximum figure for the preferred productscontemplated herein, and in general it will be found that this figurewill be lower, the actual ratio, of course, being dependent upon thevariabie factors enumerated above. For example, as will later appear, animproving agent of the preferred type in which the aliphatic substituentis derived from petroleum wax (a predominantly straight chain aliphatichydrocarbon of at least twenty carbon atoms) and in which the aromaticnucleus was derived from phenol otherwise unsubstituted may have aphenolic ratio, as expressed above, not substantially greater than aboutthirteen per cent.

A further general guide for the synthesis of the preferred improvingagents for viscous oils is to alkylate the aromatic nucleus so that itis polysubstituted with aliphatic hydrocarbon radi cals or groupspreferably of relatively high molecular weight.

As has been previously indicated, it is one of the primary objects ofthe invention to provide an oil-improving agent which will havemultifunctional improving activity in a mineral oil. Our researchindicates that compounds satisfying the requisites of general FormulaIII above may be blended in minor proportions with mineral oilfractions, particularly of the viscous or lubricating oil type, toeffect marked improvement in several important properties. Theimprovement effected may be varied somewhat with the aliphaticsubstituent, petroleum wax and allphatic hydrocarbons of similarcharacteristics such as ester wax, for example, giving products whicheffect a marked improvement in viscosity index and pour point inaddition to other prop The efiecerties to be hereinafter pointed out.tiveness may also be varied with other substituents in the arylnucleus-for example, alkoxy groups .may contribute to solubility--andthe properties of the agents may also be varied with the character ofthe metal substituent in the carboxyl group. In general it appears thatthe oilmiscible salt of. any metalsatisfying the requisites of FormulaIII above will act to inhibit oxidation in mineral oils and reduce theformation of harmful oxidation products. Certain of the metals, such,for example, as lead and zinc, may serve to increase the load-carryingcapacity of lubricating oils.

The procedure whereby the oil-improving agents contemplated by thisinvention can be prepared may be broadly described as follows:

First the hydroxyl hydrogen in an alkylated hydroxy-aromatic compound issubstituted with an alkali or alkaline earth metal to form an alkylatedaryl oxide of the corresponding alkali or alkaline earth metal which isthen carboxylated to form the alkali or alkaline earth metal salt of thealkaylated hydroxyaromatic carboxylic acid, the reactions beingindicated by the following equation:

in which M indicates an alkali or alkaline earth metal, and theremaining characters have the same significance described above inconnection with general Formula III. If it is desired to obtain a metaloxyaromatic carboxylate salt in which the carboxyl hydrogen is replacedwith alkali or alkaline earth metal the product of the .above reactionsmay be used as an intermediate starting material for reactionic) to behereinafter described.

When the desired product is one in which the carboxyl hydrogen isreplaced with some metal other than an alkali or akaline earth metal,the next step in the process involves substitution of the alkali oralkaline earth metal in the salt product of reaction (a) with thedesired metal by a process of double decomposition, such reaction beingindicated by the following equation:

in which Alk(0M) indicates the alcoholate of the metal M which may bethe same as or different, than the metal M. The metal substituents andthe hydroxyl group of in the carboxyl group metals belonging to thesilver, copper; tin,- alu-' minum, iron, alkali and alkaline earthanalytical groups, which include: silver, mercury, lead, and thallium;bismuth, copper, and cadmium; arsenic, antimony, and tin; iron, cobalt,nickel, and manganese; barium, calcium, strontium, and magnesium; andsodium, potassium, and lithium, respectively. Other desirable metalsinclude: titanium, cerium, thorium, vanadium. molybdenum, tungsten,uranium, and platinum.

the improving agents described herein may be broadly classified as theThe general reactions described and illustrated above, have shown analkylated or an aliphaticsubstituted hydroxyaromatic compound as thestarting material. Compounds of this nature, which satisfy therequirements of high alkylation for the preferred improving agentsdiscussed above, or mixtures of such compounds can be readily preparedby alkylating a mono or poly cyclic, mono or poly hydric, substituted orunsubstituted hydroxyaromatic compound with aliphatic compounds orpredominantly aliphatic materials.

The starting material for the hydroxyaromatic constituent in thealkylation reaction to obtain an alkylated hydroxyaromatic product R(T(OH)Yb)n in which Yb, if present, is residual hydrogen, may be a monoor poly cyclic hydroxyaromatic compound otherwise unsubstituted; or suchcompounds containing alkyl substituents; or in certain special cases (tobe. hereinafter described) the starting material may be an alkyl-arylether or an aralkyl-aryl ether. For obtaining an alkylatedhydroxyaromatic product containing a Y substituent, in addition to or inplace of residual hydrogen, the starting material for thehydroxyaromatic constituent may be a mono or poly cyclic hydroxyaromaticcompound in which part of the nuclear hydrogen is substituted with amember or members of the group consisting of chlorine, hydroxy, alkoxy,aroxy, aryl, alkaryl, and aralkyl groups.

Examples of the hydroxyaromatic compounds which may be used as startingmaterial for the alkylation reaction are: phenol, resorcinol,hydroquinone, catechol, cresol, xylenol, hydroxydiphenyl, benzylphenol,phenyl-ethyl-phenol,

4Q phenol resins, methyl-hydrcxydiphenyl, guaiacol.

alpha and beta naphthol, alpha and beta methyl naphthol, tolyl naphthol,xylyl naphthol, benzyl naphthol, anthranol, phenyl methyl naphthol,phenanthrol, anisole, beta naphthyl methyl ether, chlorphenol, and thelike. Preference in general is to the monohydroxy phenols otherwiseunsubstituted, particular preference being given to phenol and alpha andbeta naphthol.

The alkylation of the hydroxyaromatic compound may be accomplished invarious ways, such as by a Friedel-Crafts synthesis, using a halogenatedaliphatic hydrocarbon, or by reaction with unsaturated high molecularweight aliphatic compounds or higher alcohols in the presence of H2504as a catalyst. I

We have found the Friedel-Crafts type of alkylation reaction to beparticularly adapted to the step of preparing the alkylatedhydroxyaromatic compounds from which the improving agents describedherein are synthesized because it affords a convenient means forcontrolling the degree of alkylation andobtaining the desired phenolicratio for use in the preferred mineral oil compositions contemplated bythis invention.

In this reaction an appropriate mono or polychlorine-substitutedaliphatic compound or material is reacted with thedesired hydroxyaromatic compound in the presence of a catalytic amountof aluminum chloride. Pure or substantially pure mono or polychlorine-substituted aliphatic compounds may be used.' However,- as willbe readily understood by those skilled in the art, since it is usuallyvery diflicult to prepare or obtain high molecular weight aliphatichydrocarbons in a pure or substantially pure state and gree ofalkylation of the product.

- drocarbons, such as a suitable petroleum fraction, 5

as the starting material for our preferred improving agents, convertingit into a mixture of differentchlorine (or other halide) substitutionproducts by any suitable method for use in the alkylation step. Ingeneral it may be said that the high molecular weight aliphatichydrocarbons contemplated by this invention as preferred sources for thealkyl or aliphatic suhstituent R" in Formula III above may be pure ormixed compounds typified by .those which characterize the l heavierproducts of petroleum, such as heavypetroleum oils of the lubricanttype, petrolatum, V and crystalline petroleum wax or other compounds ormaterials which will result in relatively long chain aliphaticsubstituents. Special preference is given to petroleum wax of meltingpoint not substantially less than about 120 F. Such specially preferredaliphatic hydrocarbon materials commonly have molecular weights of about250 and have at least twenty carbon. atoms :3 in their molecules.

As stated above, the Friedel-Crafts synthesis affords a convenient meansof controlling the de- This is accomplished bycontrolling: (a) thechlorination of the aliphatic hydrocarbon and (b) the reactingproportions of the chlorinated aliphatic hydrocarbon and thehydroxyaromatic compound used in the Friedel-Crafts reaction. As is wellknown to those skilled in the art, the replacement 3.3 of nuclearhydrogen in the hydroxyaromatic compound with an aliphatic group is, inthe Friedel-Crafts synthesis, effected by reaction of such nuclearhydrogen with chlorine in the chlorinated aliphatic compound, thesubstitution in being effected with evolution of HCl. It will thus beseen that the number of chlorine substituents in a chlorinated aliphaticcompound corresponds to the number of valences (22 in general FormulaIII) which will be satisfied by or attached to hydroxyaromatic nuclei inthe product of the reaction. For example, in a reaction where a quantityof pure monochlor-aliphatic hydrocarbon containing say three atomicproportions of chlorine is reacted with one molecular proportion ofhydroxyaromatic compound, the resulting alkylated product, R"(T( OH) Yb)1],, is one in which 22 and n are equal to one and there are threealiphatic groups R attached to one nucleus T. On the other hand,assuming a reaction in which a quantity of pure trichlor-aliphatichydrocarbon containing three atomic proportions of chlorine is reactedwith one molecular proportion of hydroxyaromatic compound, the productwould be one in which 1; and n of general Formula III are each equal tothree, and the solubilizing action of a single aliphatic group would bedistributed of the aliphatic substituent R", particularly where thealiphatic substituent is a wax derivative and the agent is to be usedfor multifunctional activityin viscous oils, is not obtained withmaterials predominantly comprised of a compound or compounds R (T(OM)(CO0M')Yb)a (Formula III) ally combined or used up in the alkylation synin which 12 andn are greater than four. Hence, for use in theFriedel-Crafts reaction the chlorinated high molecular weight aliphaticmaterial should be a compound, or should be predominantly comprised ofcompounds in which the chlorine content is not greater than a tetrachlorcompound.

As will be readily. apparent to those skilled in the art, thechlorination of an aliphatic material such as a liquid petroleumfraction or a crystalline petroleum wax will normally or usually resultin a mixture of monoand poly-chlor-aliphatic hydrocarbon compounds.Consequently, the product of a Friedel-Crafts reaction between suchchlorinated material and a hydroxyaromatic compound will be a mixture ofdifierent compounds corresponding to different values of v and n in theformula R (T(OH)Yb)n and the final metal-oxyaromatic carboxylic acidsalt derived therefrom according to the reaction of Equation 0 abovewill likewise be a mixture of compounds corresponding to difierentvalues of n and v in general Formula III. It will be understood,therefore, that the specific values for v and n in the above formula, aswell as the formula itself, relate to the different specific compoundspresent in such a mixture which characterize it as a product of thepresent invention.

However, in the case of a pure compound corresponding to general FormulaIII or in mixtures thereof, We have, as previously stated, discoveredthat for a satisfactory product, the *ratio by weight of hydroxyaromaticcomponent (T(OH) )n to the corresponding alkylated hydroxyaromaticnucleus or component (R (T(.OH) )1.) should not be greater than acertain critical maximum ratio which varies with constituents,conditions of use, and properties desired, as discussed in detailhereinabove.

The above-mentioned ratio'of hydroxyaromatic component to thecorresponding alkylated hydroxyaromatic component in which thehydroxyaromatic component is calculated as phenol and which is thereforeherein referred to as the phenol content or "phenolic ratio, is usuallycalculated from the weight of the hydroxyaromatic compound used up inthe alkylation reaction and from the total weight of alkylated compoundresulting from such alkylation reaction, as will be readily understoodby those skilled in the art. For example, when the Friedel-Craftssynthesis is used for alkylation, the aliphatic hydrocarbon material isfirst chlorinated until the weight of chlorine absorbed indicates thatthe average composition of the chlorinated product comes-- ponds roughlyto say a dichlor-aliphatic hydrocarbon. Such a product will, of course,contain tracted from the weight of the alkylated oraliphatic-substituted product to obtain the weight of hydroxyaromaticmaterial ((T(OH) )n) actu- The reacting thesis. From this value and theweight of the alkylated product (R (T(OH))1.) the phenolic .ratio orphenol content can be readily calculated.

If there are other substituents (Yb) on the hydroxyaromatic nucleus inaddition to the monoor polyvalent aliphatic groups, .a deductionvshould: be made for them before calculating the phenolic ratio, anoperation which will be apparent to those skilled in the art.

In the foregoing description of the Friedel- Crafts alkylation reactionwe have referred to a hydroxyaromatic compound as a starting material.This same reaction may be used with an alkyl-aryl ether or anaralkyl-aryl ether which undergoes a substantial rearrangement during'Friedel-Crafts alkylation to form an alkylated hydroxyaromatic compoundin which the alkyl group of the ether replaces one of the nuclearhydrogen atoms.

. that the alkylation be efiected with a hydroxyaromatic compoundcontaining such alkoxy or aroxy group as a substituent and a highmolecular weight unsaturated aliphatic hydrocarbon (such as polymerizedisobutylene, dodecylene, tetradecylene, octadecylene, melene, etc.) or ahigher alcohol (such as cetyl alcohol, myricyl alcohol, ceryl alcohol,octadecyl alcohol, etc.) using H2504 as a catalyst. By this procedure,the hydroxyaromatic ether can be alkylated without substantialrearrangement taking place. As an alternative procedure, polyhydricphenols can be alkylated by reaction with alcohols or unsaturates or byFriedel-Crafts reaction follow by substitution of one hydroxy with a lowmolecular weight alkyl group. In carrying out this latter procedure, thealkylated polyhydric phenol is treated with an alkali alcoholate tointroduce alkali metal into the OH group followed by treating with thedesired alkyl halide, whereby the substitution is effected.

When it is desired to obtain a nitro or amino group as the substituentYb in general Formula III, the hydroxyaromatic compounds arealkylatedwhen free of nitro or amino groups, and such alkylation is followed bynitration of the alkylated compound to introduce the nitro substituent.The amino group can be obtained by reduction of the nitro group.

-PREPABATION or MEIALOXYABOMATIC-METAL CAR- BOXYLATE SALTS FROMWAX-SUBSTITUTED Pmnwor.

(1) Alkylation of phenol A paraflin wax melting at approximately F. andpredominantly comprised of compounds having at least twenty carbon atomsin their molecules is melted and heated to about 200 ,F., after whichchlorine is bubbled therethrough until the wax has absorbed from sixteenper cent to twenty per cent of chlorine, such product having an averagecomposition between a monochlor wax and a dichlor wax or correspondingroughly to a dichlor wax. Preferablythe chlorination is con- .tinueduntil about one-sixth the weight of the "chlqrwax formed is chlorine. Aquantity of chlorwax thus obtained, containing three (or four, withtwenty per cent chlorine in the chlorwax) atomic proportions ofchlorine, is heated to a temperature varying from just above its meltingpoint to not over F., and one mole avoid violent foaming, and duringsuch addition the temperature should be held at about 150 F. After thealuminum chloride has been added, the temperature of the mixture may beincreased slowly over a period of from fifteen to twenty-five minutes toa temperature of about 250 F. and then should be more slowly increasedto about 350 F. To control the evolution of HCl gas the temperature ofthe mixture is preferably raised from 250 F. to 350 F'. at a rate ofapproximately one degree per minute, the whole heating operationoccupying approximately two hours from the time of adding the aluminumchloride. If the emission of H01 gas has not ceased when the finaltemperature is reached, the mixture may be held at 350 F. for a shorttime to allow completion of the reaction. But, to avoid possiblecracking of the wax. the mixture should not be heated appreciably above350 F., nor should it be held at that temperature for any extendedlength of time.

It is important that all unreacted or nonalkylated hydroxyaromaticmaterial (phenol) re-. maining after the alkylation reaction be removed.Such removal can be effected generally by waterwashing, but it ispreferable to treat the waterwashed product with super-heated steam,thereby insuring complete removal of the unreacted material andaccomplishing the drying of the product in the same operation.

The wax-substituted phenol thus obtained may be characterized by thegeneral formula R (T(OH)Yh)n, in which R represents at least onealiphatic group or radical characteristic of parafiin wax having avalence v of from one to four; T represents a monocyclic aromaticnucleus; Yb represents residual hydrogen, 1) being a numbercorresponding. to the number of valences on the nucleus T not satisfiedby R and (OH) and n as a number from one to four corresponding to thevalences v on the aliphatic group or groups R which are satisfied by theI nuclear group or groups T (OH) Yb. At this step of the process, 12 inthe above general formula should always beat least one, since residualhydrogen in the nucleus is important to the car-= boxylation step to behereinafter described.

A wax-substituted phenol prepared according to the above procedure, inwhich a quantity of chlorwax containing three atomic proportions ofchlorine (sixteen per cent chlorine in the chlorwax) is reacted with onemole of phenol, may, for

go ibrevity herein, be designated as wax-phenol (3-16)! Parentheticalexpressions oi. this type (A-B) will be used. hereinafter in connectionwith the alkylated hydroxyaromatic compounds to designate (A) the numberof atomic proportions of chlorine in chlor-aliphatic material reactedwith one mole of hydroxyaromatic compound in the Friedel-Craftsreaction, and (B) the chlorine content of the chlor-aliphatic material.

In the above example A=3 and 3:16. This same designation will also applyto the metal oxyaromatic-metal carboxylate derivatives.

Wax-phenol (3-16) as obtained by the above procedure had a phenolcontent or a "phenolic ratio" of about thirteen per cent and wax phenol(4-20) had a phenolic ratio of about 12.5 per (2) Formation ofwax-substitute alkali or alkaline earth metal ph nate As an example ofthis step in the preparation of our oil-improving agents,wax-substituted sodium phenate can be prepared by the reaction ofwax-phenol with metallic sodium in the presence of a non-oxidizing gas.The reaction mixture is heated at 500 F. during a two-hour period withrapid stirring to produce finely divided sodium and thereby acceleratethe reaction. The proportions of reactants which were used in preparinga wax-substituted alkali metal phenate' according to the above procedurewere:

Grams Wax-phenol (13.2 per cent combined phenol content) 500 Sodium orequivalent amount of potassium" 16 Wax-substituted phenates of thealkali and alkali earth metals may also be prepared by reacting awax-phenol with the desired alcoholate or alkyl metal oxide of an alkalior alkaline earth metal. For this purpose anhydrous methyl and ethylalcohols are usually most suitable for use in preparing the alkyl metaloxides. As an example, 500 grams of wax-phenol (346) of 13.2 per centcombined phenol content was reacted with sixteen grams of sodium in theform of the ethyl sodium oxide by heating the mixture to about 300 F.during a one-hour period and allowing the alcohol released in thereaction to distill off, thereby obtaining the wax-substituted sodiumphenate as the final product.

(3) Carboxylation to form alkali or alkaline earth metal saltofwax-phenol carboxylic acid By rearrangement the carboxy group istransferred to the ring, giving the sodium salt of the phenol carboxylicacid:

OCOONa OH O OCOONa Other carboxylating reactions may be used in thisstep of the process, such as the reaction of is advantageous to dilutethe wax-substituted (4) Formation of the salts ofpther metals With analkali or alkaline earth metal salt, such as the sodium salt of theforegoing step, as the starting material, the corresponding salts of theother metals can be prepared by double decomposition of thefirst-mentioned salt with an alcohol-soluble inorganic or fatty acidsalt of the desired metal. The use of alcohol as a solvent for the saltis desirable to insure proper solution and reaction, the reaction beingconveniently carried out by heating the mixture at' 1'75 F. during atwo-hour period.-

The reaction product of this double decomposition or the alkali oralkaline earth metal salt obtained in the previous step is used as anintermediary for obtaining the finalmetaloxyaromatic-metal carboxylatesalt contemplated by this invention. I v

The reaction mixture employed in this double decomposition reaction may,for example, consist of one mole 'of'the sodium salt of wax-substitutedphenol carboxylic acid and one mole equivalent of the inorganic or fattyacid salt of the desired metal in alcohol solution. One part by volumeof Stoddard solvent may be employed as a diluent for the mixture. I (5),Formation of the metalomyaromatic-metal carboxylate type of salt Asillustrated by equation (0) above the salts of Formula III are obtainedby replacing-thehydroxyl hydrogen with the desired metal which with analcoholate or alkyl oxide'of the desired I metal; The alkyl oxides maybe conveniently formed by double decomposition of alkyl sodium oxidewith an alcohol-soluble salt (such as a chloride) of the desired metalto form the metal 'alcoholate and the inorganic sodium salt. A

mixture is heated during a. one-hour period at 300 F., allowing thealcohol to distill to completethe formation of the metaloxyaromaticmetalcarboxylate salt. (Formula m). The product thus obtained is separatedfrom the inorganic reaction salts, which are insoluble, by settling,filtering, or centr fu ing, without resorting to water-washing. Ifdesired, the reaction mix-.

,ture prior 'to separation, may be diluted with aid the separation ofthe salt, such separation being followed by distillation of the diluentto ,obtain the finished material. It is to be understood that theforegoing procedure is merely illustrative of the methods which may beemployed in synthesizing the various metaloxyaromatic-metal carboxylatesalts of alkylated hydroxyaromatic acids contemplated bythis invention;that polycyclic hydroxyaromatic.

compounds may be used instead of phenol and that other aliphaticcompounds or predominantly aliphatic materials may be used as the sourceof the solubilizing alkyl or aliphatic substituent (R in general Formula111.

As will appear from the foregoing description, the oil-improving agentscontemplated by this invention are characterized by the general FormulaIII (R"(T(OM) (COOM')Yb)n) described hereinabove, such compounds orproducts may also be characterized as oil-miscible alkylated oralkyl-substituted hydroxyaromatic carboxylic acids in which the hydroxyland carboxyl hydrogens have been substituted-with their equivalentweight of metal; also as the metal salts of alkylated metaloxyaromaticcarboxylic acidsfiit being understood that the terms alkyl andalkylatecl are used herein in a broad sense to include polyatomic orpolyvalent, as well as monovalent aliphatic radicals or groups.

To demonstrate the'effectiveness of compounds or products of the typedescribed above in the mineral oil compositions contemplated by this Theimproving agents used in these tests inj cludecl salts of the type abovedescribed in which both the carboxyl and hydroxyl hydrogens weresubstituted with the same metal and salts in which the carboxyl andhydroxyl hydrogens were. substituted with dilferent metals. Salts of theformer type are designated as di salts, for

example dicobaltous salt of wax phenolic acid or di-cobaltous(phenate-carboxy) salts of wax. phenolic acid. In referring tosalts ofthe latter type the hydroxyl metal substituent is indicated with thesuflix (0M) and the carboxyl metal substituent is indicated with thesuflix (COOM') Thus, for example, a salt of wax-substituted phenolcarboxylic acid in which the hydroxyl hydrogen is substituted withcopper and the carboxyl hydrogen is'substituted with sodium will bereferred to and indicated in the tables as the cupric (0M)-sodium(COOM') salt of wax phenol carboxylic acid.

' Slocum Inmnrrron This series of tests was conducted with minerallubricating oil having a Saybolt viscosity of 244 seconds at 130 F. Thetest involved subjecting the oil and various oil blends to acceleratedoxidizing conditions in the presence of metal at a temperature of 350 F.over an extended period of time, the amount of sludge formed during suchtest being expressed as the tar number.

The improvingagents used were prepared according to the procedureoutlined hereinabove.

a. suitable solvent such as a light mineral oil to highly acceleratedoxidizing conditions.

Table 1 Tar numbers on oil blends Inhibitor blended evaluated at 350with motor oil of Saybolt viscosity 1;! 244 sec.

weight 10 11 Start 7days days days 14 days None 0 1s 0u ric(OM)-so dum(COOM') salt of wax phenol carboxylic acid... Dis it or I boxy cacld$4 0 0 Cobaltous (0M)- m a n g a n o u s (COOM) salt of wax henolcarhoxyl c acid Distannous salt of wax henol carboxy 0 acid Dicohaltoussalt of wax phenol carboxyl c acid Dii'erric salt of wax phenolcarboxylc acid 4 0 0 Viscous 0 Trace Trace XXX 0 Trace 0 Viscous PoonPomr DEPRESSION In addition to the property of inhibiting sludgeformation the metal oxyaromatic-metal carboxylate salts ofwax-substituted hydroxyaromatic acids are effective pour pointdepressants,

Table II A. S. T. M. pour Depressant blended with motor oil of Saybolttests on blends viscosity of 244 sec. 130 F.

F. None +20 Cupric (OM)-sodium (COOM) salt of wax hcnol carboxylic acid10 20 Disodium salt of wax phenol carboxylic acid--. -10 -20 Cobaltous(0M)-lnanganous (COOM) salt of wax phenol carboxylic a 5 15 25 20 20OPERATION Tns'r In addition to the foregoing tests we have also madetests of an oil and an oil blend containing a representative improvingagent of the type contemplated by this invention to determine thecomparative behavior of the unblended oil and the improved oil underactual operating conditions. The test was carried out'in a singlecylinder C. F. R. engine. The engine was operated continuously over atime interval of twentyeight hours, with the cooling medium held at atemperature of about 390 F., at a speed of 1200 R. P. M., which isequivalent to a road speed of about twenty-five miles per hour. The oiltemperature was held at about E, during the test.

The oil used in this test was a lubricating oil stock of 120 seconds'Saybolt Universal viscosity at 210 F., and the conditions observed atthe end of the test were (a) the extent to which the piston rings werestuck, (b) .the extent to which the slots in the oil rings were filledwith deposit, (0) the amount of carbonaceous deposits in the oil, and(d) the acidity or neutralization number (N. N.) of the,oil at the endof the test. The oil indicated as A in Table III below is the unblendedoil and oil B is the same oil containing 4% of dicobaltous(phenate-carboxy) salt of wax phenolic acid.

Table III Ring condition Percent slots Carbon T on Degreesstuck fined(101mm NA.

. y V1!2|!34534V5 A 90 360 360 360 s60 20 so 5 18.08 2.! B so 0 4s 0 0 o0 0 5.39 0.3

droxyaromatic acid molecule, thereby taking up active oxygen and actingas a direct antioxidant; also by acting as a peptizing agent on anysludge that is formed in the oxidation of the voil; and in the event analkali or alkaline earth metal is presentas one or all of the metalsubstituents the salts act by neutralizing strong acids in the oil,particularly sulfur acids, such as may be formed by oxidation. Theimproved properties obtained and the degree of improvement in aparticular property may be varied with the metal substituents, the arylconstituents, and the degree of alkylation of the aryl nucleus.

As to the degree of alkylatlon, it is important that the aryl nucleus besufficiently alkylated to provide a final product which is soluble ormiscible in the particular mineral oil fraction with which it is to beblended, that is, one which will remain uniformly dispersed in the oilin sufiicient amount to eifect the desired improvement, under normalconditions of storage and use.

The amount of improving agent used may be varied, depending upon themineral oil or the mineral oil fraction with which it is blended and Ithe properties desiredin the final oil composition. The metaloxyaromatic-metal carboxylate salts of the type described herein may beused in amounts ranging from one-sixteenth per cent such procedures andexamples have been used for illustrative purposes only. The invention,therefore, is not to be considered as limited by the specific examplesgiven but includes within its scope such changes and modifications asfairly come within the spirit of the appended claims.

We claim:

1. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of-an oil-misciblemetaloxyaromatic-metal carboxylate salt in which part of the hydrogen ofthe aromatic nucleus has been replaced with a mineral oil solubilizingsubstituent.

2. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-misciblemetaloxyaromatic-metal carboxylate salt in which part of the hydrogen ofthe aromatic nucleus has been substituted with predominantly aliphaticorganic material, said last-mentioned substituent comprising asuflicient proportion of the substituted metaloxyaromatic-metalcarboxylate salt to render such salt miscible with said oil under normalconditions of handling and use.

3. An improved mineral oil composition comprising a mineral oil havingadmixed therewith in minor proportion: an oil-miscible wax-sub of analkyl-substituted hydroxyaromatic carboxylic acid in which both thehydroxy hydrogen and the carboxyl hydrogen are substituted with the samemetal.

6. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted hydroxyaromatic carboxylic acid in which the hydroxylhydrogen and the carboxyl hydrogen are substituted with differentmetals.

7. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted hydroxyaromatic carboxylic acid in which both thehydroxyl hydrogen and the carboxyl hydrogen are substituted with metaland in which the alkyl substituent comprises a high molecular weighthydrocarbon derivative.

8. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted hydroxyaromatic carboxylic acid in which both thehydroxyl hydrogen and the carboxyl hydrogen are substituted with metaland in which the alkyl substituent is derived from an aliphatichydrocarbon having at least twenty carbon atoms.

9. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted hydroxyaromatic carboxylic acid in which both thehydroxyl hydrogen and the carboxyl hydrogen are substituted with metaland in which the alkyl substituent is derived from petroleum wax.

10. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil miscible metal salt of analkyl-substituted hydroxyaromatic carboxylic acid in which both thehydroxyl hydrogen and the carboxyl hydrogen are substituted with metal,the alkyl substituent in said salt being a high molecular weightaliphatic hydrocarbon derivative and the aryl nucleus beingpolysubstituted with said aliphatic derivative.

11. Animproved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted hydroxyaromatic carboxylic acid in which both thehydroxyl hydrogen and the carboxyl hydrogen are substituted with metal,the alkyl substituent in said salt being derived from an aliphatichydrocarbon having at least twenty carbon atoms and the aryl nucleusthereof being poly-substituted with said aliphatic derivative.

12. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted hydroxyaromatic carboxylic acid in which both thehydroxyl hydrogen and carboxyl hydrogen are substituted with metal, thealkyl substituent in said salt being a derivative of petroleum wax andthe aryl nucleus thereof being poly-substituted with said waxderivative.

13. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted phenol-carboxylic acid in which both the hydroxylhydrogen and the carboxyl hydrogen are replaced with metal.

14. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted phenol-carboxylic acid in which both the hydroxylhydrogen and the carboxyl hydrogen are replaced with metal, the alkylsubstituent in said salt being a high molecular weight aliphatichydrocarbon derivative.

15. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted phenol-carboxylic acid in which both the hydroxylhydrogen and the carboxyl hydrogen are replaced with metal, the alkylsubstituent in said salt being a high molecular weight aliphatichydrocarbon derivative and the aryl nucleus thereof beingpoly-substituted with said aliphatic derivative.

16. 'An improved mineral oil composition ccmprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted phenol-carboxylic acid in which both the hydroxylhydrogen and the carboxyl hydrogen are replaced with metal, the alkylsubstituent in said salt being a derivative of petroleum wax.

17. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-miscible metal salt of analkyl-substituted phenol-carboxylic acid in which both the hydroxylhydrogen and the carboxyl hydrogen are. replaced with metal, the alkylsubstituent in said salt being a derivative of petroleum wax and thearyl nucleus thereof being poly-substituted with said wax derivative.

18. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of a metal salt of acarboxylated-alkylated phenol in which the hydroxyl hydrogen and thecarboxyl hydrogen are substituted with metal, the alkyl substituentbeing derived from petroleum wax and the proportion by weight of phenolin the parent alkylated-pheno] constituent being in the neighborhood ofthirteen percent.

19. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of a metal salt of acarboxylated-alkylated hydroxyaromatic compound which the hydroxylhydrogen and the carboxyl hydrogen are substituted with metal, the alkylsubstituent thereof being a derivative of petroleum wax and theproportion by weight of the hydroxyaromatic constituent in the parentalkylated hydroxyaromatic constituent being chemically equivalent to notmore than about seventeen per cent phenol.

20. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of an oil-soluble metal salt of anallgyl-substituted hydroxyaromatic carboxylic acid in which the hydroxylhydrogen and the carboxyl hydrogen are substituted with metal, saidmetal substituents being selected from metals of the silver, copper,tin, aluminum, iron, alkaline earth and alkali analytical groups.

21. An improved mineral oil composition comprising a mineral oil havingadmixed therewith a minor proportion of a product of the type obtainedby: chlorinating petroleum wax until about one-sixth of the reactionproduct is chlorine; reacting the chlorinated Wax with a hydroxyaromaticcompound in the proportion of one molof the latter to an amount of thechlorinated wax containing about three atomic proportions of chlorine toform a wax-substituted hydroxyaromatic compound; substituting thehydroxyl hydrogen thereof with metal to form a wax-substituted arylmetal oxide of. said metal; carboxylating said metal oxide to form a.metal salt of a wax-substituted hydroxyaromatic carboxylic acid; andsubstituting the hydroxyl hydrogen of said salt with a metal.

22. An improved mineral oil composition comprising a viscous mineral oilfraction having admixed therewith a minor proportion, from aboutone-sixteenth to about ten per cent of an oilmiscible alkyl -substitutedmetaloxyaromaticmetal carboxylate salt.'

23. An improved mineral oil composition comprising a viscous mineral oilfraction having admixed therewith a minor proportion, from aboutone-sixteenth to about ten per cent of an oilmiscible alkyl substitutedmetaloxyaromaticmetal carboxylate salt in which the alkyl substituent isderived from an aliphatic hydrocarbon having at least twenty carbonatoms.

24. An improved mineral oil composition comprising a viscous mineral oilfraction having admixed therewith a minor proportion, from aboutone-sixteenth to about ten per cent of an oilmiscible alkyl substitutedmetaloxyaromaticmetal carboxylate salt in which the alkyl substituent isderived from petroleum wax.

25. A composition of matter comprising a mineral oil fraction and inadmixture therwith a minor proportion of an oil miscible metalorganiccompound having the general formula:

in which: T represents an aromatic nucleus; (OM) represents at least onehydroxyl group in which the hydroxyl hydrogen is replaced with itsequivalent weight of a metal M, said group being attached to the nucleusT; (COOM') is attached to the nucleus T and represents at least onecarboxyl group the hydrogen of which is replaced by its equivalentweight of a metal M; 1'1. represents at least one aliphatic group havinga valence V of one to four, and is attached by one valence only to atleast one nucleus T; Y represents a monovalent radical selected from thegroup consisting of residual hydrogen, and chlorine, alkoxy, aroxy,aralykl, alkaryl, aryl, nitro and amino radicals; b represents thenumber of TS and is equal to zero or a whole number corresponding to thevalences on the nucleus T not satisfied by R". (OM), or (COOM); and n isa whole number from one to four; the substituent R comprising asuflicient proportion of the metalorganic' compound to render samemiscible with said oil under normal conditions of handling and use.

26. A composition of matter comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound having the general formula R"(T(OM) (COOM') Yb) n in which: Trepresents an aromatic nucleus; (OM) represents at least one hydroxylgroup in which the hydroxyl hydrogen is replaced by its equivalentweight of a metal M, said group being attached to the nucleus T; (COOM')is attached to the nucleus T and represents at least one carboxyl groupthe hydrogen of which is replaced by its equivalent weight of a metal M;R represents at least one aliphatic group having a valence v, of one tofour, and attached by one valence only to at least one nucleus T; Yrepresents a monovalent radical selected from the group consisting ofresidual hydrogen, and chlorine, alkoxy, aroxy, aralkyl, alkaryl, aryl,nitro, and amino radicals; b represents the number of Ys and is equal tozero -or a whole number corresponding to the valences on the nucleus Tnot satisfied by R", (OM) or (COOM') and n is a whole number from one tofour; the total number of carbon atoms in all of the aliphatic groupstaken together in said metalorganic compound being not less than aboutthirty for each nucleus T.

27. A composition of matter comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound having the general formula:

R"(T(OM) (COOM') Yb) n in which: T represents an aromatic nucleus; (OM)represents at least one hydroxyl group in which the hydroxyl hydrogen isreplaced with its equivalent weight of metal M, said group beingattached to the nucleus T; (COOM') is attached -to the nucleus T andrepresents at least one carvalent radical selected from the groupconsisting of residual hydrogen, and chlorine, alkoxy, aroxy, aralkyl,alkaryl, aryl, nitro, and amino radicals; b represents the number of Ysand is equal to zero or a whole number corresponding to the valences onthe nucleus T not satisfied by R",

(OM) or (COOM'); and n is a whole number 75 mama's from one to four; theequivalent ratio of T(OH) to R (T(OI-I))n in said metalorganic compoundbeing not greater than the chemical equivalent of twenty per centphenol.

28. A composition of matter comprising a mineral oil fraction and inadmixture therewith a minor proportion of an oil-miscible metalorganiccompound having the general formula: R" (T(OM) (COOM) YbRe) n in which:T represents an aromatic nucleus; (OM) represents at least one hydroxylgroup in which the hydroxyl hydrogen is replaced with its equivalentweight of metal M, said group being attached to the nucleus T; (COOM) isattached to the nucleus T and represents at least one carboxyl group thehydrogen of which isreplaced by its equivalent weight of metal M; Rrepresents at least one polyvalent aliphatic hydrocarbon group of atleast twenty carbon atoms hav- -.ing a valence 'v' of from two to four;Yb represents a monovalent radical selected from the group consisting ofresidual hydrogen, chlorine, alkoxy, aroxy, alkaryl, aralkyl, aryl,nitro, and amino radicals; 12' represents the number of Ybs and is equalto zero or a whole number corresponding to the valences'on the nucleus'1 not satisfied by R (OM), (COOM) and Re; R0 represents monovalentaliphatic radicals; 0 represents the number of Rcs and is equal to zeroor a whole number corresponding 130 the valences on the nucleus T notsatisfied by R", (OM), (COOM) and Yb; and n is a whole numbeer from twoto four.

ORLAND M. REIFF. JOHN J. GIAMMARIA. HORACE E. REDMAN.

